Electrochemical enhancement of detergent alkalinity

ABSTRACT

A device for in-situ production of caustic and increasing alkalinity of a detergent and methods for increasing alkalinity of a detergent are disclosed. In particular, in situ electrochemical conversion of bicarbonate, sesquicarbonate or carbonate sources into caustic provides a safe means for increasing alkalinity of a detergent for a variety of cleaning applications. The invention further discloses methods for cleaning using the electrochemically enhanced detergent according to the invention.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a Continuation application of U.S. Ser. No. 13/038,705 filedMar. 2, 2011, herein incorporated by reference in its entirety.

FIELD OF THE INVENTION

The invention pertains to the field of electrochemistry and moreparticularly, a device and methods for in situ electrochemicalenhancement of alkalinity through the conversion of bicarbonate,sesquicarbonate, or carbonate into caustic. In particular, a device andmethods for the electrochemical conversion of bicarbonate,sesquicarbonate, or carbonate into caustic provides a means of safelyincreasing the alkalinity of detergents and providing safe-to-handle,low pH detergent compositions for use in combination with causticgenerated in situ for a variety of cleaning applications, including forexample ware wash and laundry.

BACKGROUND OF THE INVENTION

Electrochemical cells are used for a variety of purposes. For example,electrochemical cells may be used for water treatment processes in orderto produce two forms of altered water: reduced or alkaline water andoxidized or acidic water. Electrochemical cells may also be used toproduce hypochlorite solutions or chlorine for bleaches, surfacesanitizers and other disinfectants. The electrolysis of salt to generatechlorine is also well established. In addition, electrochemical cellsare used for the conversion of sodium carbonate into sodium hydroxide.See e.g. U.S. Pat. No. 5,246,551.

Conventional electrolysis cells are equipped with at least an anode anda cathode and often have a dual structure in which the anode and cathodeare separated by one or more membranes to divide the cells intochambers, including an anode chamber and a cathode chamber. A barriermembrane provides the advantage of preventing the products in the anodechamber from mixing with the products from the cathode chamber. Variouselectrolysis cells and methods for electrolyzing water for variouspurposes are disclosed, for example in U.S. Pat. Nos. 3,616,355,4,062,754, 4,100,052, 4,761,208, 5,313,589, and 5,954,939. Dependingupon the structure of an electrochemical cell, various effluents aregenerated.

On-site production of enhanced alkalinity products such as detergentsare desirable, in order to decrease or eliminate the need to transportcaustic products and/or diluted aqueous solutions of the causticproducts which both increase the cost of transporting chemicals. Inaddition, the on-site production of enhanced alkalinity productssignificantly reduces the safety concerns associated with the transportand handling of highly alkaline cleaning compositions which presentdangers due to the caustic nature of the chemicals capable of causingburns to exposed skin, particularly in the concentrated form. As thealkalinity of the compositions increases, the possible risk to workersalso increases. Great care must therefore be taken to protect workerswho handle highly alkaline cleaning compositions. As a result, there isa need to provide in situ methods of enhancing the alkalinity ofdetergents and cleaning compositions in order to reduce or alleviatethese concerns.

Highly alkaline cleaning compositions provide the ability to clean invarious applications. For example, alkaline cleaners are effective asgrill and oven cleaners, ware wash detergents, laundry detergents,laundry presoaks, drain cleaners, hard surface cleaners, surgicalinstrument cleaners, transportation vehicle cleaning, dish washpresoaks, dish wash detergents, beverage machine cleaners, concretecleaners, building exterior cleaners, metal cleaners, floor finishstrippers, degreasers and burned-on soil removers. In a variety of theseapplications, cleaning compositions having a very high alkalinity aremost desirable and efficacious. For example, floor strippingcompositions for removal of floor finishes are most effective at ahighly alkaline pH.

Accordingly, it is an objective of the invention to formulate improvedmethods and devices for in situ production of enhanced alkalinitythrough the conversion of bicarbonate, sesquicarbonate, or carbonateinto caustic.

It is an objective of the invention to provide efficient and economicmethods for electrochemical enhancement of alkalinity withoutcoproduction of chlorine and acids.

It is a further objective of the invention to reduce the safety concernsand costs associated with transporting caustic products.

BRIEF SUMMARY OF THE INVENTION

The invention relates in general to in situ electrochemical processesfor the increase in alkalinity of detergent sources for use in a varietyof cleaning applications. More particularly, the present inventionrelates to methods for increasing alkalinity of a detergent, a devicefor in-situ production of caustic and increasing alkalinity of adetergent and a method for cleaning using an electrochemically enhanceddetergent.

According to an embodiment of the invention, a method for increasingalkalinity of a detergent includes providing an electrochemical cell,introducing an electrolyte solution to the electrochemical cell, whereinsaid solution comprises a water or detergent composition as a catholyteand an anolyte selected from the group consisting of an alkali metalcarbonate, alkali metal bicarbonate, alkali metal sesquicarbonate andmixtures thereof, and applying an electric current across the anode andcathode for electrochemical production of hydroxide and hydrogen at saidcathode and carbon dioxide and water at said anode. According to anembodiment, the electrochemical cell is configured with at least onehydrogen consuming anode, at least one hydroxide producing cathode andan ion-selective membrane.

According to further embodiments of the invention, the catholyte is adetergent composition such that the electrochemical production ofhydroxide increases the pH of the detergent to at least 10, preferablyat least 12. The detergent composition may be carbonate-free and mayfurther have a neutral pH prior to the electrochemical alkalinityenhancement. According to an alternative embodiment of the invention,the catholyte is water and a detergent composition is introduced to thehydroxide outside of the electrochemical cell in order to increase thepH of the detergent to at least 10, preferably at least 12. Thedetergent according to the embodiments of the invention provide a sourceof an alkali metal carbonate, alkali metal bicarbonate, alkali metalsesquicarbonate or mixtures thereof.

According to an embodiment of the invention, a device for in-situproduction of caustic and increasing alkalinity of a detergent includesan electrochemical cell, an electrolyte solution source comprising awater or detergent composition as a catholyte and an anolyte selectedfrom the group consisting of an alkali metal carbonate, alkali metalbicarbonate, alkali metal sesquicarbonate and mixtures thereof, and anoutlet for dispensing a product stream of either caustic or detergenthaving an increased pH of at least 10 exiting from the electrochemicalcell. According to an embodiment, the device outlet may be in fluidcommunication with a cleaning system such as a ware wash machine.

According to an embodiment the electrochemical cell is configured withat least one hydrogen consuming anode, at least one hydroxide producingcathode and an ion-selective membrane, wherein an electric current isapplied across said anode and cathode for electrochemical production ofhydroxide and hydrogen at said cathode and carbon dioxide and water atsaid anode. According to further embodiments the ion-selective membraneis a micro porous membrane, micro porous diaphragm or a cation exchangemembrane. According to additional embodiments of the invention, theanode of the electrochemical cell may be steel and said cathode istitanium.

According to an embodiment of the invention, a method for cleaning usingan electrochemically enhanced detergent includes obtaining a detergentcomposition having an increased pH of at least 10 from anelectrochemical cell and contacting an article with theelectrochemically enhanced detergent, such that the article is cleaned.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the impact of variations of electrodes and catholytesolutions on pH obtained from an electrochemical cell.

FIG. 2 shows the amperage required for most efficient pH increase in anelectrochemical cell.

FIG. 3 shows the active and total alkalinity of recirculating effluentfrom an electrochemical cell.

FIG. 4 shows the pH of the alkalinity recirculating in theelectrochemical cell with the active and total alkalinity shown in FIG.3.

FIG. 5 shows the production of caustic using a detergent source andvarious cation exchange membranes.

FIG. 6 shows the production of caustic using a detergent source andvarious anolyte solutions.

FIG. 7 shows the production of a neutral pH super-concentrate suitableto produce caustic in an electrochemical cell.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention relates to in situ electrochemical processes forthe enhancement in alkalinity of detergent sources for use in a varietyof cleaning applications. In some aspects, the present invention relatesto methods for increasing alkalinity of a detergent. In particular, themethods of in situ alkalinity enhancement allow the use of a carbonatesource to electrochemically enhance the alkalinity of the detergent. Themethods and device for performing the methods according to the inventionprovide the opportunity to convert detergents into a carbonate-freesuper concentrate product that has reduced shipping costs and usevolume. In an additional aspect, a method for cleaning using anelectrochemically enhanced detergent is disclosed. In this manner, themethods and devices of the present invention allow in-situ production ofenhanced alkalinity for on-site use and production of highly alkalinedetergents for a variety of cleaning applications, obviating the needfor transportation of highly alkaline cleaning agents.

The embodiments of this invention are not limited to particular devicesand/or methods for electrochemical enhancement of detergent alkalinity,which can vary and are understood by skilled artisans. It is further tobe understood that all terminology used herein is for the purpose ofdescribing particular embodiments only, and is not intended to belimiting in any manner or scope. For example, as used in thisspecification and the appended claims, the singular forms “a,” “an” and“the” can include plural referents unless the content clearly indicatesotherwise. Further, all units, prefixes, and symbols may be denoted intheir SI accepted form. Numeric ranges recited within the specificationare inclusive of the numbers defining the range and include each integerwithin the defined range.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which embodiments of the invention pertain. Many methods andmaterials similar, modified, or equivalent to those described herein canbe used in the practice of the embodiments of the present inventionwithout undue experimentation, the preferred materials and methods aredescribed herein. In describing and claiming the embodiments of thepresent invention, the following terminology will be used in accordancewith the definitions set out below.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities referred and variationsin the numerical quantities that can occur.

As used herein, the terms “builder,” “chelating agent,” and“sequestrant” refer to a compound that forms a complex (soluble or not)with water hardness ions (from the wash water, soil and substrates beingwashed) in a specific molar ratio. Chelating agents that can form awater soluble complex include sodium tripolyphosphate, EDTA, DTPA, NTA,citrate, and the like. Sequestrants that can form an insoluble complexinclude sodium triphosphate, zeolite A, and the like. As used herein,the terms “builder,” “chelating agent” and “sequestrant” are synonymous.

As used herein, the term “cleaning” means to perform or aid in soilremoval, bleaching, microbial population reduction, or combinationsthereof.

As used herein, the terms “feed water” and “water” refer to any sourceof water that can be used with the methods, systems and apparatus of thepresent invention. Exemplary water sources suitable for use in thepresent invention include, but are not limited to, water from amunicipal water source, or private water system, e.g., a public watersupply or a well. The water can be city water, well water, watersupplied by a municipal water system, water supplied by a private watersystem, and/or water directly from the system or well. The feed watercan also include water from a used water reservoir, such as a recyclereservoir used for storage of recycled water, a storage tank, or anycombination thereof. In some embodiments, the water source is from thesump of a mechanical washing device such as a dishwasher. In someembodiments, the water source is from a dispenser for a solid block offeedstock. In some embodiments, the water source is not industrialprocess water, e.g., water produced from a bitumen recovery operation.In other embodiments, the water source is not a waste water stream.

As used herein, the term “hard surface” includes showers, sinks,toilets, bathtubs, countertops, windows, mirrors, transportationvehicles, floors, and the like.

The term “hard water,” as used herein, refers to water having a level ofcalcium and magnesium ions in excess of about 100 ppm. Often, the molarratio of calcium to magnesium in hard water is about 2:1 or about 3:1.Although most locations have hard water, water hardness tends to varyfrom one location to another. Further, as used herein, the term“solubilized water hardness” refers to hardness minerals dissolved inionic form in an aqueous system or source, i.e., Ca⁺⁺ and Mg⁺⁺.Solubilized water hardness does not refer to hardness ions when they arein a precipitated state, i.e., when the solubility limit of the variouscompounds of calcium and magnesium in water is exceeded and thosecompounds precipitate as various salts such as, for example, calciumcarbonate and magnesium carbonate. Salts formed from water hardness ionshave low solubility in water as they are formed by metal cationsinteracting with inorganic anions. As concentration in a solutionincreases and/or temperature or pH of a water source increases, thesalts will precipitate from solution, crystallize and form hard depositsor scales on surfaces, causing the undesirable effects on equipment suchas electrochemical cells. A threshold inhibitor or threshold agent (asused synonymously) inhibits the crystallization of water hardness ionsfrom solution, without necessarily forming a specific complex with thewater hardness ion, thereby inhibiting the scaling, film and/or residuetraditionally observed in cells. Not wishing to be limited by theory, itis believed that the threshold inhibitors work by interfering with thegrowth of the scale crystals.

As used herein, the term “laundry,” refers to woven and non-wovenfabrics, and textiles. For example, laundry can include, but is notlimited to, clothing, bedding, towels and the like.

As used herein, the term “phosphate-free” or “substantiallyphosphate-free” refers to a composition, mixture, or ingredient thatdoes not contain a phosphate or phosphate-containing compound or towhich a phosphate or phosphate-containing compound has not been added.Should a phosphate or phosphate-containing compound be present throughcontamination of a phosphate-free composition, mixture, or ingredients,the amount of phosphate shall be less than about 1.0 wt-%. In someembodiments, the amount of phosphate is less than about 0.5 wt-%. Inother embodiments, the amount of phosphate is less then about 0.1 wt-%.In still yet other embodiments, the amount of phosphate is less thanabout 0.01 wt-%.

As used herein, the term “phosphorus-free” or “substantiallyphosphorus-free” refers to a composition, mixture, or ingredient thatdoes not contain phosphorus or a phosphorus-containing compound or towhich phosphorus or a phosphorus-containing compound has not been added.Should phosphorus or a phosphorus-containing compound be present throughcontamination of a phosphorus-free composition, mixture, or ingredients,the amount of phosphorus shall be less than about 1.0 wt-%. In someembodiments, the amount of phosphorous is less than about 0.5 wt-%. Inother embodiments, the amount of phosphorus is less than about 0.1 wt-%.In still yet other embodiments, the amount of phosphorus is less thanabout 0.01 wt-%.

The terms “scale,” “scaling,” “film,” and “filming” as used herein, mayexemplarily refer to either bicarbonate, carbonate, sulfate, phosphateor hydroxide scaling, caused by salts of bicarbonate, carbonate,sulfate, phosphonate and/or hydroxide with calcium, magnesium, or othermetal ions as observed in an electrochemical cell and described herein.Scaling as discussed herein and alleviated according to the thresholdagent compositions and methods of the present invention are distinctfrom cell corrosion. Corrosion of an electrochemical cell generallyrefers to the gradual weight loss of metallic components through achemical process or series of chemical reactions. Most often metals thatcome into prolonged contact with aqueous systems containing oxidants(such as chlorine, acid, bleach, caustic, etc.) are prone to corrosion.In an electrochemical cell, distinct from scaling, corrosion mostfrequently occurs at the anode due to the more acidic conditions.

As used herein, the term “solubilized water hardness” refers to hardnessminerals dissolved in ionic form in an aqueous system or source, i.e.,Ca++ and Mg++. Solubilized water hardness does not refer to hardnessions when they are in a precipitated state, i.e., when the solubilitylimit of the various compounds of calcium and magnesium in water isexceeded and those compounds precipitate as various salts such as, forexample, calcium carbonate and magnesium carbonate.

The terms “threshold agent” and “threshold inhibiting agent,” as usedherein, refer to a compound that inhibits crystallization of waterhardness ions from solution, but that need not form a specific complexwith the water hardness ion. Threshold agents are capable of maintaininghardness ions in solution beyond its normal precipitation concentration.See e.g., U.S. Pat. No. 5,547,612. This distinguishes a threshold agentfrom a chelating agent or sequestrant; however, according to theinvention the threshold agent may be either a chelating agent and/orsequestrant. Threshold agents may include, for example and withoutlimitation, polycarboxylates, such as polyacrylates, polymethacrylates,olefin/maleic copolymers, and the like. The threshold agent according tothe invention must survive the electrochemical cell's conditions toensure it is not deactivated and prevented from inhibiting scaling, andfurther must not cause any decrease in chlorine generation. As usedherein, the terms “chelating agent” and “sequestrant” refer to acompound that forms a complex (soluble or not) with water hardness ions(from the wash water, soil and substrates being washed) in a specificmolar ratio. According to the invention, the threshold agent ispreferably characterized as substoichiometric, such that the thresholdagent is effective at concentration levels that are lower than would beexpected based on a stoichiometric equivalence of the threshold agentand the scale-causing component present in the electrochemical cell ortreated water source.

As used herein, the term “ware” refers to items such as eating andcooking utensils and other hard surfaces such as showers, sinks,toilets, bathtubs, countertops, windows, minors, transportationvehicles, and floors. As used herein, the term “ware washing” refers towashing, cleaning, or rinsing ware.

The term “water soluble,” as used herein, refers to a compound that canbe dissolved in water at a concentration of more than 1 wt-%.

The term “water insoluble,” as used herein, refers to a compound thatcan be dissolved in water only to a concentration of less than 0.1 wt-%.For example, magnesium oxide is considered to be insoluble as it has awater solubility (wt %) of about 0.00062 in cold water, and about0.00860 in hot water. Other insoluble compounds include, for example:magnesium hydroxide with a water solubility of 0.00090 in cold water and0.00400 in hot water; aragonite with a water solubility of 0.00153 incold water and 0.00190 in hot water; and calcite with a water solubilityof 0.00140 in cold water and 0.00180 in hot water. The terms “slightlysoluble” or “slightly water soluble,” as used herein, refer to acompound that can be dissolved in water only to a concentration of 0.1to 1.0 wt-%.

The term “weight percent,” “wt-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

The methods, device, systems or apparatuses of the present invention caninclude, consist essentially of, or consist of the component andingredients of the present invention as well as others described hereinfor the electrochemical conversion of sources of alkalinity, includinguse of a detergent source to convert soda ash into caustic. As usedherein, “consisting essentially of” means that the methods, systems,apparatuses and compositions may include additional steps, components oringredients, but only if the additional steps, components or ingredientsdo not materially alter the basic and novel characteristics of theclaimed methods, systems, apparatuses, and compositions.

The use of electrochemistry to convert a source of sodium carbonate intosodium hydroxide is known in the art. However, according to theinvention, a neutral detergent stream may be unexpectedly used as asingle feedstock to an electrochemical cell in order to convert soda ashinto caustic, generating active alkalinity and overcoming the inabilityof those skilled in the art to produce sufficiently pure grades ofcaustic soda. Surprisingly, an alkaline source is not required for theproduction of alkalinity using the electrochemical cell and methodsaccording to the invention. According to the invention, the detergentstream (including a neutral detergent stream) provides a source ofcarbonate to be converted into caustic. According to a furtherembodiment of the invention, the detergent is introduced into anelectrochemical cell with a separate stream used as the carbonatesource. As a result, a detergent composition can be electrochemicallyenhanced so that the alkalinity of a detergent, such as a neutral pHdetergent, is increased significantly. In addition, the inventionprovides the opportunity to convert detergents into carbonate-free,super concentrated product that may subsequently be enhanced withhydroxide produced from an electrochemical cell in situ. The benefits ofthe invention significantly reduce shipping costs, enhance thealkalinity of reduced use volumes of detergent compositions and provideflexibility for the production of enhanced alkalinity detergents in situhaving desired pH ranges for particular cleaning applications.

Electrochemical Cell

The present invention provides methods and a device, system or apparatusfor increasing alkalinity of a detergent or in-situ production ofcaustic to increase the alkalinity of a detergent using anelectrochemical cell. Exemplary electrochemical units include, but arenot limited to those described U.S. Pat. Nos. 5,246,551, 5,882,501,5,906,722, 5,900,133, 5,904,829, 6,375,824, 6,569,309, 6,692,716,6,695,963, 6,913,844, 6,773,575, 6,767,447, 6,761,815 and 6,712,949. Theentire contents of each of these patents are hereby incorporated hereinby reference in its entirety. However, the methods, devices, systems orapparatus for enhancing alkalinity according to the invention is notintended to be limited according to particular structures of anelectrochemical unit. One skilled in the art understands therelationship between the structure of an electrochemical unit and theeffluents produced. For example, a unit divided by a membrane producesboth oxidizing agents and caustic. The structure of an electrochemicalcell may be adapted based upon the desired pH of the effluent accordingto the following embodiments of the invention.

According to an embodiment of the invention, the electrochemical cell isconfigured with at least one hydrogen consuming anode and at least onehydroxide producing cathode, wherein an electric current applied acrossthe anode and cathode to enable the electrochemical production ofhydroxide and hydrogen at the cathode and carbon dioxide and water atthe anode. Preferably, the anode of the electrochemical cell isconstructed of steel, stainless steel, ruthenium, or a surface coatedwith the metals. Preferably, the cathode of the electrochemical cell isconstructed of titanium, ruthenium, a Hastalloy alloy, or a surfacecoated with these metals. According to a preferred embodiment, the anodeof the electrochemical cell is constructed of steel and the cathode isconstructed of titanium. Preferably, the electrodes of theelectrochemical cell are in the form of either plates or metal screens.One skilled in the art will appreciate the numerous potential cellconfigurations (i.e. stacked plate, tubular, jelly roll, etc.) which aresuitable for use according to the electrochemical cell of the presentinvention.

According to a preferred embodiment, the electrochemical cell comprisesat least two chambers. Preferably, the at least one hydrogen consuminganode hydroxide producing cathode are separated by an ion-selectivemembrane. In a preferred embodiment, the ion-selective membrane is amicro porous membrane, a micro porous diaphragm, or a micro porousmembrane laminate, such as the Goretex membrane commercially-availablefrom G. L. Gore. In a further preferred embodiment, the ion-selectivemembrane is a cation exchange membrane capable of restricting thepassage of carbonate, bicarbonate or sesquicarbonate ions from passinginto the catholyte compartment as well as restricting the passage ofhydroxide into the anolyte compartment, while simultaneously permittingthe passage of alkali metal cations. Additional description of exemplarytypes of electrochemical cell structure suitable for use according tothe invention is disclosed in U.S. Pat. No. 5,246,551, which is hereinincorporated by reference in its entirety.

According to an embodiment of the invention, the electrochemical cell isprovided an electrolyte solution source. Preferably, the electrolytesolution comprises either a water source or a detergent composition as acatholyte. According to a further embodiment, a detergent catholyte iscarbonate-free and the cell produces hydroxide increasing the pH of thedetergent to at least 9, preferably at least 10, preferably at least 12,more preferably at least 13 at most preferably approximately 14.According to additional embodiments of the invention, a detergent isincreased to a pH of from about 9 to about 14, preferably to a pH of atleast 10. Preferably, the electrolyte solution further comprises ananolyte selected from the group consisting of an alkali metal carbonate,alkali metal bicarbonate, alkali metal sesquicarbonate and mixturesthereof.

The electrolyte solution source according to the invention may beprovided by a single source (i.e. single input stream) or a doublesource (i.e. double input stream) into the electrochemical cell.According to an embodiment, the electrolyte solution source may beprovided to the electrochemical cell by a single input stream of adetergent composition, wherein the detergent provides a source of analkali metal carbonate, alkali metal bicarbonate, alkali metalsesquicarbonate and mixtures thereof for both the anolyte and catholyte.According to a further embodiment of the invention, the electrolytesolution source may be provided to the electrochemical cell by a double(or multiple) input stream, wherein the catholyte is a water source andthe anolyte is a source of an alkali metal carbonate, alkali metalbicarbonate, alkali metal sesquicarbonate and mixtures thereof.

In discussing the various embodiments of the invention the production ofcaustic (or caustic soda) shall be understood to refer to sodiumhydroxide. According to the invention and the various embodiments of theinvention, one skilled in the art will understand that the reference toproduction of caustic or sodium hydroxide shall also refer to thespecific products relating to the particular electrolyte solutionsutilized. For example, the methods and devices described herein areintended to relate to the detergent compositions and/or sources ofalkali metal carbonate, alkali metal bicarbonate, alkali metalsesquicarbonate and mixtures thereof. The alkali metals include forexample, sodium, potassium and lithium. According to an embodiment ofthe invention, alkali metal hydroxides and hydrogen are produced at thecathode and water and carbon dioxide are produced at the anode as shownby the following chemical reactions:

(Cathode) 2H₂O→2OH⁻+H₂

(Anode) Na₂CO₃+H₂→2Na⁺+H₂O+CO₂

(Overall) Na₂CO₃+H₂O→2NaOH+CO₂

Device

According to an embodiment of the invention a device for in-situproduction of caustic and increasing alkalinity of a detergent isdisclosed. The device may comprise, consist of or consist essentially ofan electrochemical cell with an electrolyte solution source for theelectrochemical cell, wherein the electrolyte solution comprises a wateror detergent composition as a catholyte and an anolyte selected from thegroup consisting of an alkali metal carbonate, alkali metal bicarbonate,alkali metal sesquicarbonate and mixtures thereof, and an outlet fordispensing a product stream of either caustic or detergent.

According to the invention, the electrochemical cell may be configuredaccording to the various embodiments disclosed herein, including thepreferred embodiments of having at least one hydrogen consuming anode ofsteel, at least one hydroxide producing titanium cathode and anion-selective membrane, wherein the membrane is a micro porous membrane,micro porous diaphragm or a cation exchange membrane, wherein anelectric current is applied across said anode and cathode forelectrochemical production of hydroxide and hydrogen at said cathode andcarbon dioxide and water at said anode.

According to certain embodiments of the invention, the device may becombined with a dispenser in fluid communication with theelectrochemical cell. According to an embodiment, the dispenser providesan electrolyte solution comprising a detergent composition with a sourceof an alkali metal carbonate, alkali metal bicarbonate, alkali metalsesquicarbonate or combinations to be provided to the electrochemicalcell.

According to a further embodiment the outlet from the device may be influid communication with a cleaning system to provide an enhancedalkalinity detergent composition. According to such an embodiment, thedispenser provides a detergent composition having a pH of at least 10,preferably at least 12 as a result of the caustic increasing thealkalinity of said detergent composition.

According to a still further embodiment of the invention, the outletfrom the device may be in fluid communication with a dispenser housing adetergent composition to be combined with the caustic produced by theelectrochemical cell to provide to a cleaning system an enhancedalkalinity detergent composition having a pH of at least 10, preferablyat least 12. According to this embodiment of the invention, thedetergent composition may be carbonate-free and essentially a neutralpH, such that the increased pH is a result of the electrochemicalproduction of hydroxide combined with the detergent composition.

Alternatively, the device may be combined with a dispenser that is amodified detergent dispenser, wherein an electrochemical cell isbuilt-in to such dispenser. According to a further embodiment, a washingmachine or other washing system has an electrochemical cell built-in. Insome embodiments, the washing system is selected from the groupconsisting of a ware washing system, a laundry washing system, a vehiclewashing system, a clean in place washing system, and combinationsthereof.

According to an embodiment of the invention, modifications to the devicecomprising the electrochemical cell may be made. A cell modification maycomprise, consist of or consist essentially of the use of air injectionto reduce the power demand of a cell. According to an embodiment of theinvention, an oxygen-containing gas or source, such as air, may bepassed through a chamber of a cell to decrease voltage requirementsand/or increase chemical generation from a cell. Further description ofthis embodiment is disclosed in related application Ser. No. ______(Attorney Docket Number 2794US01), entitled Bubbling Air Through anElectrochemical Cell to Increase Efficiency. The entire contents of thispatent application are hereby expressly incorporated herein by referenceincluding, without limitation, the specification, claims, and abstract,as well as any figures, tables, or drawings thereof.

Methods of Enhancing Alkalinity

According to an embodiment of the invention, a method for increasingalkalinity of a detergent includes providing an electrochemical cellconfigured with at least one hydrogen consuming anode, at least onehydroxide producing cathode and an ion-selective membrane, introducingan electrolyte solution into the electrochemical cell, and applying anelectric current across the anode and cathode for electrochemicalproduction of hydroxide and hydrogen at said cathode and carbon dioxideand water at said anode. According to the embodiments of the invention,the electrolyte solution may include either a water or detergentcomposition as a catholyte solution an alkali metal carbonate source,alkali metal bicarbonate source, alkali metal sesquicarbonate source ormixtures thereof as the anolyte solution.

The methods of enhancing alkalinity according to the invention convert asource of carbonate, bicarbonate or sesquicarbonate into caustic. As setforth in the various embodiments of the invention, a detergent streammay be used as a single feedstock to an electrochemical cell in order toconvert soda ash into caustic. According to a further embodiment of theinvention, the detergent may be introduced into an electrochemical cellwith a separate stream used as the carbonate source. As a result, adetergent composition can be electrochemically enhanced so that thealkalinity of a detergent, such as a neutral pH detergent, is increasedsignificantly.

The methods of enhancing alkalinity according to the invention furtherallow the use of caustic generated from carbonate in situ to be combinedwith a separate detergent use stream. According to this embodiment, thenewly formed caustic may be stored, for example at a point of use in asump, or immediately combined with a detergent composition to providesuch detergent with enhanced alkalinity. As a result, the inventionprovides the opportunity to convert detergents that are carbonate-free,super concentrated products into a highly alkaline composition as aresult of the combination of hydroxide produced in situ by anelectrochemical cell with a neutral pH detergent.

According to embodiments of the invention, the method for increasingalkalinity of a detergent result in an increase of pH of detergentcomposition to at least 10. More preferably, the methods for increasingalkalinity of a detergent result in an increase of pH of a detergentcomposition to a pH of at least 12. According to a further embodiment,the detergent composition may be carbonate-free and/or have a neutralpH.

Methods of Use

According to an embodiment of the invention, a method for cleaning usingan electrochemically enhanced detergent is disclosed and includesobtaining a detergent composition having an increased pH of at least 10from an electrochemical cell and contacting an article with theelectrochemically enhanced detergent, such that the article is cleaned.According to a further embodiment, a method for cleaning using anelectrochemically enhanced detergent includes contacting a detergentcomposition with a source of alkalinity having an increased pH obtainedfrom an electrochemical cell and contacting an article with theelectrochemically enhanced detergent. The detergent composition ispreferably a neutral pH detergent, wherein the pH of the detergent isincreased to at least 10, preferably at least 12, with the addition ofthe electrochemically produced caustic composition.

The enhanced alkalinity detergent or caustic solution to be combinedwith a detergent composition is provided to at least one article orsystem in need of cleaning. According to an embodiment of the invention,an article or articles to be cleaned are contacted with a use solutionobtained according to the methods of the invention, such that thearticle(s) is cleaned. In some embodiments, the method further comprisesrinsing the article. The article can be rinsed with treated water,treated softened water, or with untreated water. A rinse aid can also beapplied to the article after it has been washed.

Any automatic or manual washing system that would benefit from the useof the methods according to the present invention can be used. Theseinclude a variety of industrial (commercial) and domestic (residential)applications. For example, a method, system, or apparatus of the presentinvention can be to provide either alkalinity or enhanced alkalinitydetergents to be used in: ware washing applications, e.g., washingeating, instruments and cooking utensils; in hard surfaces cleaning,such as showers, sinks, toilets, bathtubs, countertops, windows, minors,and floors; in laundry applications, e.g., automatic textile washingmachines; in vehicle care and carwash applications; industrialapplications; in food service and food processing applications; inbottle washing applications; in clean-in-place applications; and inhealthcare instrument care applications, such as surgical instrumentcleaning.

In some embodiments, the methods of cleaning according to the inventioncan be applied at the point of use. A point of use may include anycleaning application wherein pH adjustment of a use solution ordetergent is desired. For example, a method, system, device or apparatusof the invention can be applied to a water source upstream of anapplication such as a washing system. In some embodiments, the water ispassed through the one or more cleaning components immediately prior tothe desired end use of the water source. For example, an apparatus ofthe invention could be employed to a water line connected to a householdor restaurant appliance, e.g., a dishwashing or ware washing machine. Inaddition, the system, device or apparatus employing the methods of thepresent invention may be located in a washing system.

A device, apparatus or system according to embodiments of the inventionmay be used with a washing system in a variety of ways. In someembodiments, the device, apparatus or system may be connected to adetergent dispensing device, such that a neutral detergent compositionis combined with the caustic source to provide an on-site generatedenhanced alkalinity detergent composition. The device, apparatus orsystem may be used to supply water containing an enhanced alkalinitydetergent (such as a use solution of an enhanced alkalinity detergentcomposition) to a washing system. In some embodiments, the device,apparatus or system may be used to supply a mixture of water, enhancedalkalinity detergent composition and/or an additional ingredient(s),e.g., surfactant, to a washing system.

In Situ Cleaning System

An electrochemical cell according to the present invention may beprovided with an in situ cleaning system, as further described in U.S.Ser. No. 12/887,755 (Attorney Docket Number 2574USU1), entitled In-SituCleaning System. The entire contents of this patent application arehereby expressly incorporated herein by reference, including, withoutlimitation, the specification, claims, and abstract, as well as anyfigures, tables, or drawings thereof. The electrochemical cell accordingto the invention may be provided within an in situ cleaning systemcomprising, consisting of or consisting essentially of a water treatmentcomponent (such as a threshold agent, catalytic system, conversionagents, resin materials and filtration systems). According to anadditional embodiment of the invention, the electrochemical cellaccording to the invention may be provided within an in situ cleaningsystem comprising, consisting of or consisting essentially of a watertreatment component and an alkalinity generating components (such as adecomposition agent).

Water Treatment Component

According to an embodiment of the invention, the in situ cleaning systemcomprising an electrochemical cell further comprises, consists of orconsists essentially includes a water treatment component. A watertreatment component is provided to the system, for example, to reducethe amount of solubilized hardness in a water source. Without beinglimited to a particular theory, the water treatment component reducessolubilized hardness in water, thereby reducing the amount of oreliminating the need for chelating agents, sequestering agents,conventional builders, chelating agent, threshold agents and/orphosphorous needed in a detergent or cleaning agent supplied to awashing system according to the invention. As a result, use of a watertreatment component in the in situ cleaning systems according to theinvention minimizes the amount of chemicals added to the resultingcleaning agent compared to non-treated water sources and increases theefficacy of the cleaning agent. In addition, use of a water treatmentcomponent according to the invention reduces the amount of hard waterdeposits, scales, and build up occurring on surfaces contacted by a feedwater, providing an additional benefit of reducing the need to clean thein situ cleaning system itself.

Suitable water treatment components for use in the methods and systemsaccording to the invention may include for example, threshold agentsystems, catalytic systems, conversion agent systems, resin materials,filtration systems, and/or alkaline sources, as are each describedfurther in this application. Preferred embodiments of the inventionemploying water treatment components do not require softening water.According to an embodiment, water treatment components according to theinvention reduce a source of solubilized water hardness in the feedwater. Preferred embodiments provide unsoftened water for use in the insitu cleaning systems of the invention. Preferred embodiments of theinvention include the use of an unsoftened water source that issubsequently treated by one or more of the following water treatmentcomponents as described according to the invention.

Threshold Agents

Threshold agents may be used according to the device and methods of thepresent invention in order to minimize or eliminate the failure ofelectrodes and membranes of the electrochemical cells caused by bothcorrosion and hard water scaling. It is well understood that thelongevity of electrodes and membranes of electrochemical cells aresignificantly diminished due to scaling and/or corrosion. See e.g., U.S.Pat. No. 4,248,690. Most often, calcium and magnesium ions are containedin either the water source or salt solutions added to electrochemicalcells, resulting in the previously considered unavoidable scaling incells, resulting in detrimental effects to the cells by forminghydroxide precipitates and scale. The precipitate and scale eventuallycoat the surface of the electrodes and membranes causing an increasedvoltage demand by the cell and may potentially lead to short-circuitingof the cell. The device and methods of the present invention overcomethese significant disadvantages to using electrochemical cells alongwith eliminating the need to use softened water, chelating agents and/orsequestrants through the use of a threshold agent. Further descriptionof threshold agents suitable for use according to the present inventionis disclosed in U.S. Ser. No. 12/986,312 (Attorney Docket Number2697USU1), entitled Control of Hard Water Scaling in ElectrochemicalCells. The entire contents of this patent application are herebyexpressly incorporated herein by reference, including, withoutlimitation, the specification, claims, and abstract, as well as anyfigures, tables, or drawings thereof.

The threshold agent utilized according to the invention prevents thescaling of the electrodes and membranes in electrochemical cells, namelythe cathode of a cell. According to a preferred embodiment, thethreshold agents according to the invention are water soluble polymericsystems capable of preventing hard water scale formation on bothelectrodes and resin or ceramic membranes. According to the invention,the threshold agents are compatible for inhibiting scaling caused byhard water deposits, particularly in systems supplied with water havinghigh levels of carbonate, hydroxide and/or phosphate ions along withwater hardness ions traditionally leading to buildup in cells causingthe unsightly residue, film and scaling that is detrimental to cells.According to an embodiment of the invention, water impurities such ascalcium and magnesium are not deleterious to the electrolytic water oncethreshold agents are utilized to prevent crystallization and scalingwith bicarbonate, carbonate, hydroxide, sulfate and/or phosphate ions.Accordingly, use of the threshold agent of the present inventionobviates the need to “soften” the water source used in anelectrochemical cell.

According to a preferred embodiment, the threshold inhibiting agents maybe a polycarboxylate or related copolymer. Polycarboxylates refer tocompounds having a plurality of carboxylate groups. A variety of suchpolycarboxylate polymers and copolymers are known and described inpatent and other literature, and are available commercially. Exemplarypolycarboxylates that may be utilized as threshold inhibiting agentsaccording to the invention include for example: homopolymers andcopolymers of polyacrylates; polyacrylates; polymethacrylates;noncarboxylated materials such as polyolefinic and polymaleiccopolymers, such as olefinic and maleic hydride copolymers; andderivatives and salts of all of the same.

Suitable polycarboxylates and related copolymers according to theinvention may include water soluble polycarboxylate polymers, includingfor example homopolymeric and copolymeric agents. Additional suitablepolycarboxylates may include homopolymeric and copolymeric agents, suchas polymeric compositions with pendant (—CO₂H) carboxylic acid groups,including polyacrylic acid, polymethacrylic acid, polymaleic acid,acrylic acid-methacrylic acid copolymers, acrylic-maleic copolymers,hydrolyzed polyacrylamide, hydrolyzed methacrylamide, hydrolyzedacrylamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile,hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrilemethacrylonitrile copolymers, or mixtures thereof. According to afurther embodiment, the water soluble salts or partial salts of thesepolymers and copolymers may further be suitable threshold agentsaccording to the invention. Additional description of exemplarypolycarboxylates is provided in U.S. Pat. No. 7,537,705.

Examples of oligomeric or polymeric polycarboxylates suitable asthreshold agents include for example: oligomaleic acids as described,for example, in EP-A-451 508 and EP-A-396 303; co- and terpolymers ofunsaturated C4-C8-dicarboxylic acids, possible co-monomers which may bepresent being monoethylenically unsaturated monomers from group (i) inamounts of up to 95% by weight, from group (ii) in amounts of up to 60%by weight, from group (iii) in amounts of up to 20% by weight. Examplesof suitable unsaturated C4-C8-dicarboxylic acids include maleic acid,fumaric acid, itaconic acid and citraconic acid. Suitable co- andterpolymers are disclosed, for example, in U.S. Pat. No. 3,887,806.

The group (i) includes monoethylenically unsaturatedC3-C8-monocarboxylic acids, such as acrylic acid, methacrylic acid,crotonic acid and vinylacetic acid, for example acrylic acid andmethacrylic acid. Group (ii) includes monoethylenically unsaturatedC2-C22-olefins, vinyl alkyl ethers with C1-C8-alkyl groups, styrene,vinyl esters of C1-C8-carboxylic acids, (meth)acrylamide andvinylpyrrolidone, for example C2-C6-olefins, vinyl alkyl ethers withC1-C4-alkyl groups, vinyl acetate and vinyl propionate. Group (iii)includes (meth)acrylic esters of C1-C8-alcohols, (meth)acrylnitrile,(meth)acrylamides of C1-C8-amines, N-vinylformamide and vinylimidazole.

Suitable polyacrylates, homopolymers and copolymers of polyacrylates,polyolefinic and polymaleic systems for threshold agents according tothe invention may include organic compounds, including both polymericand small molecule agents, including for example polyanioniccompositions, such as polyacrylic acid compounds. Polymeric agentscommonly comprise polyanionic compositions such as polyacrylic acidcompounds. Polymers such as Acusol 448 (Rohm & Haas) and others arecommercially available and may be useful according to the presentinvention. For example, exemplary commercially available acrylic-typepolymers include acrylic acid polymers, methacrylic acid polymers,acrylic acid-methacrylic acid copolymers, and water-soluble salts of thesaid polymers. These include polyelectrolytes such as water solubleacrylic polymers such as polyacrylic acid, maleic/olefin copolymer,acrylic/maleic copolymer, polymethacrylic acid, acrylic acid-methacrylicacid copolymers, hydrolyzed polyacrylamide, hydrolyzedpolymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers,hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile,hydrolyzed acrylonitrile-methacrylonitrile copolymers, hydrolyzedmethacrylamide, hydrolyzed acrylamide-methacrylamide copolymers, andcombinations thereof. Such polymers, or mixtures thereof, include watersoluble salts or partial salts of these polymers such as theirrespective alkali metal (for example, sodium or potassium) or ammoniumsalts can also be used. The weight average molecular weight of thepolymers is from about 2,000 to about 20,000. According to a preferredembodiment, the threshold agent for use in the compositions and methodsof the present invention is the commercially-available Acumer 1000.

According to an additional embodiment of the invention, sulfonatedpolymers may be used as the threshold agent for inhibiting scaling in anelectrochemical cell. These may include a variety of sulfonated polymersand copolymers, such as for example, carboxylic sulfonated polymers andcopolymers, carboxylic sulfonated nonionic terpolymers, sulfonatedstyrene/maleic acid copolymers and various other sulfonated polymers andcopolymers as may be ascertained by those of ordinary skill in the artto which the invention pertains. Examples of suitable commerciallyavailable threshold agents include, for example: Acusol 588 and Acusol420 (all available from Rohm & Haas).

One skilled in the art will understand the methods of synthesis of suchpolymers and co-polymers if commercially available threshold agents arenot utilized. It is to be understood according to the threshold agentsdescribed herein, that such polymers refer to compositions produced bypolymerization of one or more monomers with no restriction on the numberof types of monomers incorporated in the polymer. Further it is to beunderstood that co-polymers refer to compositions produced according toa variety of known methods of polymerization with no restriction on thenumber of types of monomers incorporated in the polymer.

Although not intending to be limited according to a particular theory,the threshold agents suitable for use according to the present inventionare preferably short chain polymers with low molecular weights that donot cause decreased chlorine production or increased voltage demand as aresult of a large molecular weight and long chain interfering withelectrical flow in an electrochemical cell. According to an embodimentof the invention, suitable threshold agents have a molecular weight lessthan at least 5,000, more preferably less than 4,000, more preferablyless than 3,000 and according to a most preferred embodiment less than2,000.

According to an additional embodiment of the invention, the thresholdagent may be a water-insoluble resin. For example, a threshold agent maybe obtained as the result of running water over a water-insoluble resinto release a water soluble polymeric threshold agent, such as a resinbead. A commercially-available resin bead is available from Dow® underthe tradename Amberlyte IRC-76®, which represents a preferred embodimentof the invention. Additional suitable water-insoluble resins forgenerating threshold agents in a water source treated by anelectrochemical cell are disclosed in U.S. Ser. No. 12/764,621 filed onApr. 21, 2010 entitled “Methods and Apparatus for Controlling WaterHardness” (Attorney Docket No. 2699USU1), the entire content of which ishereby incorporated by reference.

It is expected that other types of scale inhibitors meeting therequirements described herein according to the invention can be includedwith the threshold agent according to the invention, if desired.Particularly, additional scale inhibitors may be added to handle aparticular type of scaling in a given application or environment, suchas a unique water supply. One skilled in the art will ascertain the needfor such additional scale inhibitors according to the invention.

It is desirable to provide the threshold agent in a concentration thatis sufficient to provide a desired level of scale inhibition. Accordingto the invention, the ratio of threshold agent to be added to ahypochlorite or chlorine-containing oxidant source or the ratio ofthreshold agent added to an electrochemical cell producing hypochloritemay vary. According to an embodiment, the threshold agent can beprovided at a concentration up to about 10,000 ppm to achieve a desiredlevel of scale inhibition. According to a preferred embodiment, thethreshold agent can be provided at a concentration up to about 5,000 ppmor up to about 1,000 ppm. According to a still further preferredembodiment, the threshold agent can be provided in concentrations fromabout 50 to about 500 ppm. According to particular embodiments a mostpreferred concentration to provide a desired level of scale inhibitionmay be about 100 ppm threshold agent. According to the invention, theeffective amounts of threshold agents utilized refers to an amountsufficient to provide an inhibitory effect on the water scaling in anelectrochemical cell as compared with an identical composition andelectrochemical cell that does not contain a sufficient amount of thethreshold agent to inhibit such water scaling.

The threshold agent composition according to the invention may beformulated into a variety of composition formulations, such as forexample a solid or a flowable liquid. According to one embodiment, thecomposition is incorporated into the salt feed for the electrochemicalcell, forming a solution with the water source upon entry into the cell.The formulation of the threshold agent with the salt may be in either aflowable liquid incorporated into the salt feed for the electrochemicalcell or solid form. According to an alternative embodiment, the solidcomposition may be a block, powder, or other pelleted material.According to an additional embodiment, the solid threshold agent may beprovided in a block formulation to be added to an electrochemical cellfor a slow or extended time-release of the threshold agent in a cell.Alternatively, the threshold agent may be introduced into the water feedfor the electrochemical cell in either a solid or flowable liquid.According to further embodiments of the invention, the threshold agentmay be added directly into the electrochemical cell as a separate feedfrom the water or salt.

Various threshold agent compositions are disclosed as embodiments of theinvention. According to one aspect of the invention, a threshold agentmay comprise, consist of or consist essentially of about 50 ppm to about10,000 ppm of a threshold agent and may be combined with a catholyteand/or anolyte source, such as water or a detergent according to theinvention. The threshold agent according to the invention is a watersoluble polymeric system capable of preventing hard water scaleformation on electrodes and membranes, preferably a polycarboxylateselected from the group consisting of homopolymers and copolymers ofpolyacrylates, polyolefinic systems, polymaleic systems, derivatives andsalts of the same, and combinations of the same. According to apreferred embodiment, the polycarboxylate is Acumer 1000. The thresholdagent may further be a product of rinsing a water insoluble resin withwater.

According to the invention, the threshold agent may be formulated into avariety of composition formulations, such as for example a solid or aflowable liquid. In one embodiment, the threshold agent is added in theform of a liquid. In another embodiment, the threshold agent is in theform of a solid block which is then dispensed into a stream of waterusing a variety of solids dispensing systems known to the art. In anadditional embodiment, the threshold agent is combined with the chemicalfeed for the electrochemical cell (for example, sodium chloride, sodiumbicarbonate, and sodium carbonate). In another embodiment, the source ofthe threshold agent is from a weak cation exchange resin which has hadits cation exchange capability exhausted by exposure to a source ofcalcium or magnesium or mixtures thereof. Exemplary exhausted weakcation exchange resins which can serve as a source of threshold agent tocontrol water hardness are described in U.S. patent application Ser. No.12/764,621 filed on Apr. 21, 2010, entitled “Methods and Apparatus forControlling Water Hardness” (Attorney Docket No. 2699USU1), the entirecontent of which is hereby incorporated by reference.

Catalytic Systems

According to additional embodiments of the invention, the watertreatment component can include a catalytic system. Exemplary watertreatment components including catalytic agents, systems and methods ofusing the same to reduce solubilized water hardness are described inU.S. patent application Ser. No. 12/764,606 filed on Apr. 21, 2010,entitled “Catalytic Water Treatment Method and Apparatus” (AttorneyDocket No. 2580USU1), the entire content of which is hereby incorporatedby reference.

An embodiment of a catalytic system for use as a water treatmentcomponent according to the invention includes a treatment reservoirincluding one or more catalysts positioned therein. In some embodiments,the catalyst includes a water treatment agent bound to a supportingmaterial, wherein the water treatment agent is selected from the groupconsisting of a source of magnesium, zinc, titanium and iron ions andcombinations of the same. Optionally, the catalyst may include a sourceof aluminum. Optionally, the catalyst may be zinc-free.

Any material capable of supporting the water treatment agent can be usedin the catalyst system for the water treatment component. Supportingmaterial may be provided in any shape and size, including, beads,sheets, rods, disks or combinations of more than one shape. In addition,the catalyst may be bound to the support material in a variety of ways.For example, in some embodiments, the supporting material comprises aresin which may include, but is not limited to, a weak acid cation resin(e.g., an acrylic acid polymer, a methacrylic acid polymer, and mixturesthereof), a polymer having sulfonic acid substituents, a carboxylic acidpolymer, and mixtures thereof. The catalyst can be ionically bound tothe support medium in some embodiments, as well as combined with unboundadditional ingredients. Additional function ingredients may be combinedwith the catalysts for use in the water treatment component, in anyform, including for example metal oxides, metal hydroxides, polymorphsof calcium carbonate (non-calcite forms) and combinations and mixturesthereof.

The catalyst system for use with as a water treatment componentaccording to an embodiment of the invention can be contained in atreatment reservoir. The reservoir may be any shape or size appropriatefor the use of the water and the volume of water to be treated,including for example, a tank, a cartridge, a filter bed of variousphysical shapes or sizes, or a column. In some embodiments, thetreatment reservoir may be pressurized or non-pressurized.

Conversion Agents

According to additional embodiments of the invention, the watertreatment component can include a treatment reservoir including one ormore conversion agents. Without wishing to be bound by any particulartheory, it is thought that the conversion agents for use with themethods of the present invention cause solubilized calcium waterhardness ions in water to substantially precipitate in a non-calcitecrystalline form via an interfacial reaction that produces thethermodynamically unfavorable crystal form aragonite, rather than as thethermodynamically favorable crystal form calcite. Thus, contacting feedwater with a conversion agent according to an embodiment of theinvention reduces the solubilized water hardness of the treated water,and leads to a reduction in scale formation on a surface in contact withthe treated water. The aragonite crystals can also act as seed crystalsfor further reduction of solubilized calcium after contacting theconversion agent.

Exemplary water treatment components including conversion agents, suchas water soluble magnesium compounds, and methods of using the same aredescribed in U.S. patent application Ser. No. 12/114,448, entitled“Water Treatment System and Downstream Cleaning Methods” (AttorneyDocket No. 2428USU1) and U.S. patent application Ser. No. 12/114,513,entitled “Cleaning Compositions Containing Water Soluble MagnesiumCompound and Method of Using Them” (Attorney Docket No. 2488USU1), theentire contents of which are hereby incorporated by reference.

In some embodiments, the conversion agent may be a solid particle.Conversion agents suitable for use with the present invention include,but are not limited to metal oxides, metal hydroxides, polymorphs ofcalcium carbonate and combinations and mixtures thereof. In someembodiments, the conversion agent includes a metal oxide. Metal oxidessuitable for use in the present invention include, but are not limitedto, magnesium oxide, aluminum oxide, titanium oxide, and combinationsand mixtures thereof. Optionally, the conversion agent is free ofaluminum. Optionally, the conversion agent is free of zinc. Metalhydroxides suitable for use with the present invention include, but arenot limited to, magnesium hydroxide, aluminum hydroxide, titaniumhydroxide, and combinations and mixtures thereof. Polymorphs of calciumcarbonate suitable for use as a conversion agent include, but are notlimited to, aragonite. In some embodiments, magnesium oxide, magnesiumhydroxide, or a combination of magnesium oxide and hydroxide are used asa conversion agent to treat water. The conversion agent may be in anyform, e.g., solid, particle, liquid, powder, nanoparticle, slurry,suitable for use with the methods and in situ cleaning systems of thepresent invention.

Certain embodiments of the invention use a magnesium source for thewater treatment component. The composition can include magnesium ion atpredefined ratios to calcium ion in water, such as magnesium ion in amolar amount equal to or in excess over a molar amount of calcium ion.It is preferred the water soluble magnesium salt can include an anionthat, together with calcium ion, forms a water soluble calcium salt. Forexample, the present invention may include a soluble magnesium sourceprovided to the feed water. According to an embodiment of the invention,use of a water soluble magnesium (a hardness ion (Mg²⁺)) as a watertreatment component works at least as well as a conventional chelatingagent or sequestrant (i.e. sodium tripolyphosphate (STPP)) at preventingprecipitation of calcium salts while actually increasing the overallwater hardness.

Suitable water soluble magnesium compounds include those selected fromthe group consisting of magnesium acetate, magnesium benzoate, magnesiumbromide, magnesium bromate, magnesium chlorate, magnesium chloride,magnesium chromate, magnesium citrate, magnesium formate, magnesiumhexafluorosilicate, magnesium iodate, magnesium iodide, magnesiumlactate, magnesium molybdate, magnesium nitrate, magnesium perchlorate,magnesium phosphinate, magnesium salicylate, magnesium sulfate,magnesium sulfite, magnesium tartrate, magnesium thiosulfate, a hydratethereof, and a mixture thereof. These salts can be provided as hydratedsalts or anhydrous salts. Water soluble magnesium compounds approved asGRAS for direct food contact, including for example, magnesium chlorideand magnesium sulfate, can also be used.

The water treatment component including a conversion agent can furtherinclude additional functional ingredients. Additional functionalingredients suitable for use include any materials that impartbeneficial properties to the conversion agent, the water source beingtreated, or any combination thereof. For example, in some embodimentsthe conversion agent includes a solid media bed of particles, e.g.,magnesium oxide particles. Additional functional ingredients may beadded that aid in the prevention of “cementing” of the media bed, i.e.,agglomeration of the particles, as it is contacted with a water source.In still further embodiments, the additional functional ingredientincludes a polymorph of calcium carbonate. Exemplary polymorphs ofcalcium carbonate include, but are not limited to, aragonite, calcite,vaterite and mixtures thereof. In other embodiments, the additionalfunctional ingredient includes a mixed cation compound of calcium andmagnesium ions. In some embodiments, the additional functional materialincludes calcium magnesium carbonate, some natural minerals of which mayalso be known by the name dolomite.

The conversion agent for use with the water treatment componentaccording to the invention can be contained in a treatment reservoir inthe water treatment component. The reservoir can be for example, a tank,a cartridge (such as a portable removable cartridge), a filter bed ofvarious physical shapes or sizes, or a column. In some embodiments, thetreatment reservoir including a conversion agent is resin-free, viz., itdoes not contain a material that contains univalent hydrogen, sodium orpotassium ions, which exchange with divalent calcium and magnesium ionsin the water source. The reservoir can be pressurized or notpressurized. One reservoir or multiple reservoirs can be used. Forexample, the water source can be passed over a plurality of reservoirs,in the same or in separate containers, comprising the same or differentconversion agents. The reservoirs may also be arranged in series or inparallel.

In some embodiments, the conversion agent is in the form of an agitatedbed or column. The bed or column can be agitated to avoid “cementing,”i.e., agglomeration of the solid conversion agent once contacted withthe water source. The bed or column can be agitated by any known methodincluding, for example, by the flow of water through the column,fluidization, mechanical agitation, high flow backwash, recirculation,and combinations thereof. In some embodiments, the solid conversionagent includes a fluidized bed, e.g., a column or a cartridge, in thetreatment reservoir. Fluidization is obtained by an increase in thevelocity of the fluid, e.g., water, passing through the bed such that itis in excess of the minimum fluidization velocity of the media. In stillfurther embodiments, the treatment reservoir comprises a portable,removable cartridge.

Resin Materials

In additional embodiments of the invention, the water treatmentcomponent may include a resin material to control water hardness withoutsubstantially altering the water source. A variety of resin materialsmay be used with the in situ cleaning systems of the present inventionand embodiments are described in U.S. patent application Ser. No.12/764,621 filed on Apr. 21, 2010 entitled “Methods and Apparatus forControlling Water Hardness” (Attorney Docket No. 2699USU1), the entirecontent of which is hereby incorporated by reference.

Various embodiments of the resin material may be incorporated into thewater treatment component of the in situ cleaning system, including forexample, exhausted resin materials, a resin substantially loaded with aplurality of one or more multivalent cations, substantially waterinsoluble resin material and acid cation exchange resin. In someembodiments, the resin material is an exhausted resin material. As usedherein, the term “exhausted resin material” refers to an ion exchangeresin material that can control water hardness, but that is incapable ofperforming an ion exchange function. In some embodiments, an exhaustedresin material has a surface that is substantially loaded with aplurality of one or more multivalent cations, and is thus unable toexchange ions with a water source when contacted with a water source.The exhausted resin materials of the present invention do not controlwater hardness through an ion exchange mechanism. That is, the surfaceof an exhausted resin material is inert, as it is loaded with aplurality of multivalent cations.

In additional embodiments, the resin is substantially loaded with aplurality of one or more multivalent cations, which may include amixture of calcium and magnesium ions. The calcium and magnesium ionsmay be loaded on to the resin material at a ratio of from about 1:10 toabout 10:1, about 1:5 to about 5:1, about 1:3 to about 3:1, about 1:2 toabout 2:1, or from about 1:1 of calcium ions to magnesium ions. In stillfurther embodiments, a substantially water insoluble resin material isloaded with a plurality of cations.

Additional embodiments of the resin materials for the water treatmentcomponent include an acid cation exchange resin that may include a weakacid cation exchange resin, a strong acid cation exchange resin, andcombinations thereof. Weak acid cation exchange resins suitable for usein the present invention include, but are not limited to, a cross linkedacrylic acid polymer, a cross linked methacrylic acid polymer, andmixtures thereof. In some embodiments, resin polymers have additionalcopolymers added. The copolymers include but are not limited tobutadiene, ethylene, propylene, acrylonitrile, styrene, vinylidenechloride, vinyl chloride, and derivatives and mixtures thereof.

The resin material for use in the invention may be provided in any shapeand size, including beads, rods, disks or combinations of more than oneshape. In some embodiments, the resin material is selected from thegroup consisting of a gel type resin structure, a macroporous type resinstructure, and combinations thereof. In some embodiments, the resinmaterial may have a particle size of from about 0.5 mm to about 1.6 mmand to as large as 5.0 mm. The resin material may also include a mixtureof particle sizes, viz. a mixture of large and small particles. It isalso to be understood that the resin material is contained within atreatment reservoir in some embodiments, wherein any reservoir capableof holding the water treatment composition may be used as a treatmentreservoir.

Filtration Systems

According to additional embodiments of the invention, the watertreatment component may include filtration systems. Any suitablefiltration systems can be used in the in situ cleaning system for watertreatment according to the invention. Filtration systems, including forexample, ionic filtration systems, may be used to remove precipitatesfrom feed water.

Alkalinity Generating Components—Decomposition Agents

According to an embodiment of the invention, the in situ cleaning systemcomprising an electrochemical cell further comprises, consists of orconsists essentially includes an additional alkalinity generatingcomponent. According to an embodiment of the invention, an alkalinitygenerating component for further generation of alkalinity may includesany device or component capable of producing a source of alkalinity orresulting in an increase in the pH of a treated use solution, includingfor example a decomposition agent capable of catalyzing thedecomposition of an oxidizing agent to form a source of alkalinity.Suitable decomposition agents and systems for alkalinity generatingcomponents according to the invention are further described U.S. patentapplication Ser. Nos. 12/780,407 (Attorney Docket No. 2532USU1) and12/780,453 (Attorney Docket No. 2532USU2) entitled “Compositions,Systems and Method for In Situ Generation of Alkalinity,” and 12/780,503(Attorney Docket No. 2532USU3) entitled “Peroxygen Catalyst-ContainingFabric and Use for In Situ Generation of Alkalinity,” the entirecontents of which are hereby incorporated by reference.

Without wishing to be bound by any particular theory of the invention,the decomposition agent catalyzes the decomposition of a peroxygensource that may be produced by an electrochemical cell, generatingalkalinity. The decomposition agent may further facilitate thedecomposition of the peroxygen source, preferably a dilute peroxygensource. Still further, the decomposition agent causes bubbling usefulfor improved cleaning, such as removal of soil from hard surfaces.Production of alkalinity in situ allows for the use of cleaningcompositions, such as cleaning concentrates, having decreased levels ofalkalinity in applications which require higher levels of alkalinity asthe decomposition agent and the peroxygen source can be brought intocontact, generating alkalinity at the desired time of use.

The decomposition agent according to the invention may include varioussubstances as well as the use of one or more decomposition agents for acleaning composition. The decomposition agent according to the inventionis not consumed by the reaction with the peroxygen source. Accordingly,it is an embodiment of the invention that the decomposition agent doesnot need to be replaced and is be reusable in combination with varioussupport media. In some embodiments, the decomposition agent may haveactivity as a bleach activator in the presence of a bleachable substrateand as a decomposition agent for the increase of alkalinity from thedecomposition of a peroxygen source in the absence of a bleachablesubstrate. In further embodiments, the decomposition agent of thereduced alkalinity cleaning composition is metallic. Examples ofdecomposition agents include various forms of metallic manganese,silver, and vanadium.

According to preferred embodiments the decomposition agent includes atleast one source of manganese. In some embodiments, the manganese sourceis derived from manganese metal, manganese oxides, colloidal manganese,inorganic or organic complexes of manganese, including manganesesulfate, manganese carbonate, manganese acetate, manganese lactate,manganese nitrate, manganese gluconate, manganese chloride orcommercially available as Dragon A350 (also known as Dragon's Blood,available from Rahu Catalystics of Nottingham, U.K.), or any of thesalts of salt forming species with manganese.

According to a further preferred embodiment, the decomposition agentincludes at least one source of silver. In some embodiments, the silversource is derived from silver metal, silver oxides, silver hydroxide,colloidal silver, inorganic or organic complexes of silver,water-soluble or insoluble silver salts, including silver sulfate,silver carbonate, silver acetate, silver lactate, silver nitrate, silvergluconate, or silver chloride, or any of the salts of or salt formingspecies with silver. According to a still further embodiment, thedecomposition agent includes at least one source of vanadium.

According to the invention, the decomposition agent is substantiallyfree of iron, which may slow down the rate or counteract the activity ofthe decomposition agent according to the invention. In some embodiments,the decomposition agents may be soluble in water, slightly soluble inwater, form a suspension in water or insoluble in water. According tofurther embodiments, the decomposition agent is provided in its solid,naturally occurring form. For example, the metallic silver decompositionagent according to an embodiment of the invention may be provided as asolid piece of silver. In other embodiments, the decomposition agent canbe deposited onto or into a catalyst support matrix.

According to the invention, increasing the concentration of thedecomposition agent results in a faster rate of pH increase. In someembodiments of the invention, the decomposition agent has aconcentration in a cleaning composition without a support medium fromabout 0.5 ppm to about 10 wt-%. In some embodiments, the decompositionagents are present at about 1 ppm to about 5 wt-%, or from about 50 ppmto about 2 wt-%. In further embodiments of the invention, thedecomposition agent has a concentration in a cleaning composition whenpresent on a support medium from about 1 wt-% to about 100 wt-%. In someembodiments, the decomposition agents are present at about 5 wt-% toabout 50 wt-%, and in other embodiments at about 10 wt-% to about 30wt-%. It is to be understood that all values and ranges between thesevalues and ranges are encompassed by the invention. According to afurther embodiment, one or more promoters may be used in combinationwith a decomposition agent. Decomposition promoters suitable for usewith the present invention include, but are not limited to, a magnesiumion source, a copper ion source, a zinc ion source, and mixturesthereof.

In some embodiments, the decomposition agent is provided on a supportmedium. Any support medium, i.e., substrate, which is compatible withthe selected decomposition agent can be used. For example, the supportmedium can include, but is not limited to, a fabric, a pad, a sponge, aninorganic particle, a foam, and combinations thereof. The support mediumcan be any water insoluble inert support such as a support bed, forexample. For example, the support bed can include a source of captive,water insoluble alkalinity. Additional examples of the support mediumcan include, but are not limited to, magnesium oxide, magnesiumhydroxide, zinc oxide, titanium oxide, aluminum oxide, silicon oxide,alumino-silicate, ceramic, or polymeric material. The decompositionagent can be adhered to the support medium by any means known in theart. For example, the decomposition agent can be adhered to the supportmedium by physical absorption or by ionic exchange. According to otherembodiments, the decomposition agent is bound to or adhered to a fabric.Examples of fabric which can be used include sponges, non wovenmaterials, woven materials, cotton or other natural sources, polyester,polyamide, polyolefin, extruded films and laminates. The decompositionagent can be adhered to the fabric by any means known in the art.

Other suitable support media include particles that have been loadedwith the decomposition agent. Exemplary particles include, but are notlimited to, carbon, ion exchange resin, silicates, sand, aluminum oxide,metal oxides, and/or combinations thereof. Metal oxides suitable for usein the methods of the present invention include zinc oxide, magnesiumoxide, titanium oxide, and combinations thereof. In some embodiments,the support medium is substantially free of aluminum oxide. In someembodiments, the decomposition agent may be provided in a cartridge or acolumn in the alkalinity generating component. The cartridge includesone or more inlets and one or more outlets and contains thedecomposition agent. The cartridge can also include the support mediumto which the decomposition agent can be bound. The decomposition agentcan also be loose within the cartridge. In some embodiments, thecartridge contains fibers which include the decomposition agent, such asloose fibers of silver.

Additional Ingredients

Embodiments of the invention may further include an additionalingredient inlet in fluid communication with the in situ cleaningsystem, such as the outlet. Any ingredient which would be useful for aparticular washing system or method of use according to the inventionmay be used. The additional ingredient used in embodiments of theinvention may be a liquid or a solid. For example, the additionalingredient can include, but is not limited to, one or more of thefollowing: inorganic additives; builders, e.g., chelating/sequesteringagents; threshold agents, organic additives; surfactants; rinse aids;bleaching agents (oxy- or active halogen); bleach catalysts;sanitizers/antimicrobial agents; activators; defoaming agents;solidification agents; anti-redeposition agents; optical brighteners;dyes; odorants; hardening agents; solubility modifiers; corrosioninhibitors; magnesium sources or resins (water soluble or insoluble);enzymes and combinations thereof, as well as a variety of othermaterials, depending upon the desired characteristics and/orfunctionality of the cleaning agent for use in the washing systemaccording to the invention.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated by reference.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.

Example 1 Comparison of Cell Set-Ups for Conversion of Soda Ash intoCaustic

A two compartment cell was set-up in a variety of ways to determine thetypes of electrodes to be used in each chamber of an electrochemicalcell. A two compartment cell was set-up using titanium and stainlesssteel as the electrode pair and Nafion 324 (commercially available fromDupont®) as the cation exchange membrane. The amps were fixed at 4A andthe resulting voltage allowed to float.

Both water and an aqueous solution of 20% soda ash were eluted throughthe different sides of the cell to determine the best catholyte sourcefor the cell. As the water and an aqueous solution of 20% soda ash wereeluted through the different sides of the cell the changes in pH of thewater monitored. The titanium was most effective as the cathode andstainless steel as the anode. As shown in FIG. 1, the pH increase of thewater was maximized when water was utilized as the catholyte.

Example 2

The preferred cell design of Example 1 (titanium cathode and water ascatholyte) was further evaluated to determine the power required for thedesired increase in pH. The amperage of the titanium cathode/watercatholyte system of Example 1 was further evaluated to determine theamount of amps needed to provide the most efficient pH increase. Asshown in FIG. 2, between 3-5 amps provided nearly equivalent and equallyeffective increases in pH (exceeding pH 12) using the cell design ofExample 1. According to the tested system, 3 amps provides the amount ofpower at which there is a diminishing return for a system.

Example 3

The preferred cell design of Examples 1 and 2 (titanium cathode andwater as the catholyte at 4 amps) was evaluated to determine the rate ofalkalinity increase versus the type of alkalinity produced. FIG. 3 showsa graph of the type of alkalinity produced by the electrochemical cell.Active alkalinity is measured by a titration for sodium hydroxide,whereas total alkalinity is measured by a titration for sodium hydroxideand carbonate. The measurements were taken regardless of the productionrate and show that nearly all of the alkalinity produced according tothe invention is active alkalinity. FIG. 4 shows the pH of therecirculating effluent obtained from the same electrochemical cell.

Example 4 Generation of Alkalinity in a Ready to Use Ware Wash Detergent

The preferred electrochemical cell design and conditions of Examples 1-3were used to generate alkalinity in a 2000 ppm use solution of APEX LP®ware wash detergent (commercially available from Ecolab®). APEX LP® is asolid ware wash detergent with approximately 65-68% soda ash. The 2000ppm use solution of APEX LP® ware wash detergent, representative of adetergent concentration used for various cleaning applications,including ware wash applications, was substituted for the water(catholyte) in Examples 1-3. The anolyte was 20% sodium carbonate.

Various membranes were tested according to the electrochemical celldesign and conditions of Examples 1-3. Nafion 324, Nafion 424 and Nafion117 cation exchange membranes were tested to determine the impact of thedetergent on the various cation exchange membranes. FIG. 5 shows thegeneration of caustic proceeded well with a ware wash detergent solutionsubstituted for the catholyte water stream of Examples 1-3. The pH ofthe APEX LP® ware wash detergent increased from approximately 11 toapproximately 13 using the electrochemical cell to enhance the detergentalkalinity according to the invention demonstrating the ability of theinvention to increase the alkalinity of detergent compositions.According to an embodiment of the invention a detergent composition issuitable for use with a dispenser to provide to an electrochemical cellaccording to the invention.

Example 5 Comparison of Sodium Carbonate Vs. Sodium Bicarbonate in Readyto Use Solution of Ware Wash Detergent

The methods of Example 4 were replicated using a Nafion 324 cationexchange membrane and 4 amps (allowing voltage to float). A saturatedsolution of sodium bicarbonate (approximately 10%) was substituted forthe 20% sodium carbonate anolyte of Example 4. FIG. 6 shows that eithersodium bicarbonate or sodium carbonate can be used to generate in situalkalinity in a detergent solution. In addition, it is expected thatmixtures thereof can further be used to generate in situ alkalinity in adetergent solution.

Example 6 Generation of Alkalinity in a Laundry Detergent Sump Solution

Example 4 was replicated using the Nafion 324 cation exchange membrane.A 10% sump solution of a laundry detergent, Formula 1 (commerciallyavailable from Ecolab®) was used in place of the ready to use APEX LP®ware wash detergent. Formula 1 is an aqueous slurry ware wash detergentwith approximately 20% soda ash (as opposed to the approximately 65-68%soda ash in APEX LP®). The decreased concentration of soda ash in thedetergent formulations did not result in any decrease in pH of causticproduced according to the electrochemical cell and methods of theinvention. However, increased voltage demand was observed with thedecreased concentration of soda ash.

The experimentation further demonstrated that sodium bicarbonate can beused as a soda ash source. As shown, the carbonate source incorporatedinto the detergent was not converted; rather the bicarbonate (orcarbonate) on the other side of the electrochemical cell was converted.As shown by FIG. 7, the electrochemical cell rapidly generated causticwhich increased the alkalinity of the sump solution.

It was further demonstrated in FIG. 7 that the approximately 20% sodaash in the Formula 1 detergent could be removed without impacting therate of alkalinity increase in the detergent. The soda ash was removedfrom one formulation of the Formula 1 ware wash detergent causing the pHof the detergent to decrease from approximately 11 to approximately 8.The same enhanced alkalinity detergent was produced for both sources ofFormula 1 used in the electrochemical cell, resulting in a producthaving a pH of approximately 13. In effect, this allows the in situpreparation of an alkaline detergent from a neutral pHsuper-concentrate.

1. A method for increasing alkalinity of a detergent comprising: (a)providing an electrochemical cell configured with at least one hydrogenconsuming anode, at least one hydroxide producing cathode and anion-selective membrane; (b) introducing an electrolyte solution intosaid electrochemical cell, wherein said solution comprises water or adetergent composition as a catholyte and an anolyte selected from thegroup consisting of an alkali metal carbonate, alkali metal bicarbonate,alkali metal sesquicarbonate and mixtures thereof; and (c) applying anelectric current across said anode and cathode for electrochemicalproduction of hydroxide and hydrogen at said cathode to increase the pHof said detergent composition and carbon dioxide and water at saidanode.
 2. The method of claim 1 wherein said catholyte is a detergentcomposition and said electrochemical production of hydroxide increasesthe pH of said detergent to at least
 10. 3. The method of claim 2wherein said detergent composition is carbonate-free and has a neutralpH.
 4. The method of claim 1 wherein said catholyte is a detergentcomposition and said electrochemical production of hydroxide increasesthe pH of said detergent to at least
 12. 5. The method of claim 4wherein said detergent composition is carbonate-free and has a neutralpH.
 6. The method of claim 1 wherein said catholyte is water and furthercomprising introducing said hydroxide produced by said electrochemicalcell to a detergent composition outside of said electrochemical cell,wherein said hydroxide increases the pH of said detergent to at least12.
 7. The method of claim 1 wherein said electrolyte solution is adetergent comprising an alkali metal carbonate, alkali metalbicarbonate, alkali metal sesquicarbonate or mixtures thereof.
 8. Themethod of claim 1 further comprising adding a threshold agent to saidelectrochemical cell in the amount of up to about 10,000 ppm, whereinsaid threshold agent is a water soluble polycarboxylate having amolecular weight less than 5,000 selected from the group consisting ofhomopolymers and copolymers of polyacrylates, polyolefinic systems,polymaleic systems, derivatives and salts of the same, and combinationsof the same.
 9. The method of claim 1 further comprising adding at leastone additional component to said electrolyte solution or detergentcomposition selected from the group consisting of a builder, thresholdagent, surfactant, rinse aid, bleaching agent, bleach catalyst,sanitizer or antimicrobial agent, defoaming agent, solidification agent,anti-redeposition agent, optical brightener, dye, odorant, hardeningagent, solubility modifier, corrosion inhibitor, magnesium sources orresins, enzyme or combinations thereof.
 10. A device for in-situproduction of caustic and increasing alkalinity of a detergentcomprising: (a) an electrochemical cell configured with at least onehydrogen consuming anode, at least one hydroxide producing cathode andan ion-selective membrane, wherein an electric current is applied acrosssaid anode and cathode for electrochemical production of hydroxide andhydrogen at said cathode to increase the pH of a detergent compositionemployed as a catholyte and carbon dioxide and water at said anode; (b)an electrolyte solution source for said electrochemical cell, whereinsaid solution comprises water or a detergent composition as a catholyteand an anolyte selected from the group consisting of an alkali metalcarbonate, alkali metal bicarbonate, alkali metal sesquicarbonate andmixtures thereof; and (c) an outlet for dispensing a product stream ofeither caustic or detergent having an increased pH of at least 10exiting from the electrochemical cell.
 11. The device of claim 10wherein said ion-selective membrane is a micro porous membrane, microporous diaphragm or a cation exchange membrane.
 12. The device of claim10 wherein said anode is steel and said cathode is titanium.
 13. Thedevice of claim 10 further comprising a dispenser in fluid communicationwith said electrochemical cell, wherein said dispenser provides anelectrolyte solution comprising a detergent composition with a source ofan alkali metal carbonate, alkali metal bicarbonate, alkali metalsesquicarbonate or combinations thereof.
 14. The device of claim 10further comprising a dispenser in fluid communication with said outletand product stream of caustic, wherein said dispenser provides adetergent composition, wherein said caustic increases the alkalinity ofsaid detergent composition to a pH of at least 12, and wherein saidoutlet is in fluid communication with a cleaning system such as a warewash machine.
 15. The device of claim 10 wherein said catholyte is adetergent composition that is carbonate-free and said electrochemicalproduction of hydroxide increases the pH of said detergent to at least12.
 16. The device of claim 10 wherein said electrolyte solution furthercomprises a threshold agent in the amount of up to about 10,000 ppm,wherein said threshold agent is a water soluble polycarboxylate having amolecular weight less than 5,000 selected from the group consisting ofhomopolymers and copolymers of polyacrylates, polyolefinic systems,polymaleic systems, derivatives and salts of the same, and combinationsof the same.
 17. The device of claim 10 wherein said electrolytesolution or detergent composition further comprises a source of abuilder, threshold agent, surfactant, rinse aid, bleaching agent, bleachcatalyst, sanitizer or antimicrobial agent, defoaming agent,solidification agent, anti-redeposition agent, optical brightener, dye,odorant, hardening agent, solubility modifier, corrosion inhibitor,magnesium sources or resins, enzyme or combinations thereof.
 18. Amethod for cleaning using an electrochemically enhanced detergentcomprising: (a) obtaining a detergent composition having an increased pHof at least 10 from an electrochemical cell, said cell comprising: (i)at least one hydrogen consuming anode, at least one hydroxide producingcathode and an ion-selective membrane, wherein an electric current isapplied across said anode and cathode for electrochemical production ofhydroxide and hydrogen at said cathode to increase the pH of a detergentcomposition and carbon dioxide and water at said anode; (ii) anelectrolyte solution source for said electrochemical cell, wherein saidsolution comprises a detergent composition with a source of an alkalimetal carbonate, alkali metal bicarbonate, alkali metal sesquicarbonateor mixtures thereof; (iii) an outlet for dispensing a product stream ofan electrochemically enhanced detergent having a pH of at least 10; and(b) contacting an article with said electrochemically enhanceddetergent, such that the article is cleaned.
 19. The method of claim 18wherein said detergent composition provided as an electrolyte solutionis carbonate-free and has a neutral pH.
 20. The method of claim 18wherein said detergent composition obtained from said electrochemicalcell has a pH of at least 12.